Oil, grease, and hydrocarbon resistant material



Patented July 4, i939 UNITED STATES PATENT OFFICE OIL, GREASE, ANDHIDROOABBON RESIST- TEBIAL ANTHA No Application December 19, 1938,Serial No. 116,825

1 Claim. ((11. 91-48) This invention relates to oil, grease andhydrocarbon resistant material, particularly to oil, grease andhydrocarbon resistant fibrous materials, and more particularly tofibrous materials 5 carrying as a coating a flexible film, which isimpervious to oils, greases and hydrocarbons, such as gasoline and thelike.

The use of disposable non-refillable containers for lubricating oils andpanicularly motor oils has become quite common in recent years. Themajority of such containers are made of tinned sheet metal, but thesecontainers are relatively expensive, diflicuit to seal because of thetendency of the oil to creep on the metal surface and dimcult to disposeof conveniently. Moreover, when such containers are emptied, aconsiderable portion of the oil remains within them due to its highattraction for the metal surface, entailing waste.

It has recently been proposed to use fibrous containers such ascontainers made from paper, pulp, or the like, in place of the metalcontainers heretofore used... Such containers are relatively inexpensivebeing made from cheap materials,

such as pressed waste newspaper pulp, and are easily disposed of afteruse. Such containers are;

of course, nbrmally highly pervious to hydrocarbons, such as motor oil,and therefore, to be usable, must be provided with a flexible,inexpensive lining which is permanently impervious to oil. Certaincoating compositions have been proposed for use in this connection, butso far as known, none of them is entirely successful.

The principal object or this invention is the production of aninteriorly coated fibrous container which is highly suitable formerchandising of oils, greases and hydrocarbons.

Another object of this invention is to make an oil, grease andhydrocarbon resistant material with inexpensive fibrous materials as thebase,

and to provide therefor an inexpensive oil, grease and hydrocarbonimpervious flexible lining.

Another object of this invention is to-accomplish the foregoing objectsby a simple and economical process.

Other objects will be apparent to those skilled in the art as thedescription of this invention proceeds.

In the practice of the invention, there is first provided a fibrousmaterial, such as fiber board,

cardboard, paperboard, cloth, or pressed paper pulp, and the like. Thus,it it isdesired to make a container from pressed paper pulp, beatenpaper pulp is pressed into the shape of the finished container byspinning or blowing into molds of de- 5 sired shape. Such molds may beformed trom wire screen or other foraminous or porous material, as iswell understood in the art of fabricating paper pulp. A suitablecontainer may be made from preformed cardboard or paperboard 10 ifdesired. Thus, sheet paper, cardboard, paperboard, pulpboard, cloth,asbestos board, asbestos paper, or the like, may be subjected to thetreatment below described and supplied to the trade for use whereveroil, grease and hydrocarbon resistant fibrous material is desired, orfor the subsequent fabrication of containers therefrom by the usualmethods known in the paper manufacture art, such as folding,cutting,'and adhering with an oil, grease and hydrocarbon resistant ad-20 hesive which has an adhesive attraction for the treated surfaces ofthe product. Within the purview 01 the invention, there may be used theuntreated, uncoated materials above enumerated or' such materials whichhave been treated or coated 25 with other substances than those shownbelow, as, for instance, rubber-impregnated or rubbercoated paper orcloth, which, oi-course, is sub ject to extremely high deteriorationwhen left in contact with oils, greases and hydrocarbons.

By the term hydrocarbon as used in this specification and claim, it isintended to include all organic compounds containing as elements onlycarbon and hydrogen, including all saturated ali- ,phatic hydrocarbons,such as gasoline, petroleum 35 naphtha, benzene, ligroin, kerosene,spindle oil,

' petroleum oil, such as lubricating and motor oil,

Sid

to solid'an'd even gaseous hydrocarbons. Thus. material treated bytheprocess herein disclosed might be used for the retention of gaseoushydrocarbons such as in gas-holders, gas tanks, etc.

By the term oil and grease-resistant" as used in this specification andclaim, there is; con-. templated resistance to oily and greasyhydrocarbons included in the above enumeration, as well as resistance tovegetable and animal oils such as peanut butter, mayonnaise, linseedoil, hydrogenated cottonseed oil and to the higher fatty acids such asstearic acid, oleic acid, etc. In general, by the term oil, grease andhydrocarbon-=resistant there is contemplated resistance to any oily orgreasy or hydrocarbon material;

It has been discovered that by the application of a plurality ofcoatings to the fibrous base material to be rendered oil, grease andhydrocarbon resistant, at least one of which coatings is a cellulosederivative and at least one oi which is a water-miscible organic bindersuch as glue or wateresoluble gums fiexibilized with cert sugars eitheralone or in combination with polyhydric alcohols, that the resultingmaterial is highly impervious to hydrocarbons, oils and are and retainsthe imperviousness indefinitely. ere

may be use only the two coatings referred to,

or other coatings in addition.

, To form the cellulose derivative coating, there is employed as coatingmaterial the usual lac que'r' made up of the cellulose derivative, suitable solvents therefor, and suitable plasticizers and softeners, but. itis preferred to use an aqueous emulsion of a cellulose derivative or ofa cellulose derivative lacquer. As cellulose derivative, cellulosenitrate, cellulose acetate, ethyl cellulose, etc., may be used, butcellulose nitrate is preferred. A suitable formula for the emul sionwhich is preferred is given in the examples below, but it is to beunderstood that other formulae and proportions may be used and that anycoating of a cellulose derivative is deemed to fall within the spirit ofthis invention. The

coating is produced by any appropriate coating process. Thus, in thecase of a pressed pulp container, cellulose derivative solution oremulsion may be poured into the interior and the container rotated whileemptying it, allowing it to drain drip-free and drying thoroughly.prefer-=- abiy under forced draft conditions, and at elevatedtemperature.

As the water-miscible organic binder there may be used any of theprotein glues, such as albumin, casein, soya bean casein, zein, gelatin,animal glue, hide glue or bone glue, although animal, hide or bone glueare preferred, or there may be used any of the water-soluble gums suchas gum karaya, gum tragacanth, gum arable (gum acacia), dextrine(British gum), etc. To

render this film flexible there is incorporated in I the initial coatingcomposition a water-soluble sugar or a sugar syrup, such as thetrisaccharides, such as raflinose, the disaccharides, such as sucrose(cane sugar), lactose, maltose, the monosaccharides, such as mannose,glucose, invert sugar (dextrose and levulose) fructose, galactose,arabinose, xylose, rhamnose. etc, or syrups of any of these sugars. Forcheapness it'ls preferred to use the cheaper, more available sugars suchFilms made from the water-miscible binder above described flexibilizedwith these sugars are exceedingly impervious to hydrocarbons.

The sugars are less effective flexibilizing agents than the polyhydricalcohols, although they impart suflicient flexibility for many purposes.If desired, however, greater. flexibility may be secured by usingsuitable proportions of the polyhydric alcohols with the sugars incompounding the water-miscible organic binder coating. Such "preferredto we a ratio of one to two parts of flexibiliner to one part of thebinder.

The fie xibilized coating may be applied by any mown coating process.Thus, it may be applied to preformed containers in the same manner asabove descri for the cellulose derivative coating, but it is preferableto heat it before coating with it.

Oil, grease and hydrocarbon resistance is obtained in the productwhether there is first ap-' plied the cellulose derivative coating,followed by the fiembilized water-miscible organic coating, or whetherthe-coatings are applied in the reverse order with the nembilizedwater-miscible organic coating next to the base material and eposedthereupon the cellulose derivative coating. However, the first mentionedorder is preferred, especially when using an aqueous cellulosederivative lacquer emulsion on a fibrous base since the water of theemulsion is taken up the porous material very rapidly, resulting in ahigh adherence of the lacquer, and a very much shortened drying time. isnecessary ore the fiexibilized coating is applied. Moreover, containersso prepared in which the oilrepellant coat is in direct contact with thehydrocarbon oil drain more completely on emptying.

-The flexibilized water-miscible organic binder coat shows such a highadherence to the cellulose derivative undercoat that the two coatscannot be separated. The cellulose derivative undercoat protects thewater-miscible organic film from atmospheric moisture or dryness whichmight penetrate through the fiber base, while the water-miscible organiccoating protects the cellulose derivative undercoat from contact withthe oii,grease or hydrocarbon material which might tend to dissolve theplasticizer therefrom, resulting in leakage. Thus, it i seen that thedissimilar coats described cooperate in a new and novel manner andproduce results which would not be obtainable with two cellulosederivative coats or two water-miscible organiccoats. Moreover. a moreeconomical coating is obtained using the coatings described. However,with water-miscible organic binder as the first coat, and cellulosederivative as the second coat, many of the advantages of the inventionare attained and the container will not fail altogether in humidclimates.

When reference is made to sorbitol, there is also contemplated atechnical grade of sorbitol syrup prepared by the catalytichydrogenation or electrolytic reduction of glucose and which may containas impurities some 'unreduced glucose, ash and salts of organic acids.

In the following examples there are set forth several preferredembodiments of the invention.

It is to be understood, however, that the inv tion is not limitedthereto.

Exmu l Coating'A (cellulose derivative) Water phase, 28%% by weight Percent by weight Water 99 Sulfonated castor oil (75% grade) 1} 8811 Gramsper gallon 5 Sodium salt of sulfonated lauryl alcohol extracted withmethyl alcohol (Duponol Me) i 19 Methyl cellulose (Tylose 5-25) 11.1

Lacquer phase, Il by weight liquids, 1 gallon.

Per cent by volume Octyl acetat 7 m b Butyl acetate 25 Butyl alcohol 10Toluol 2i Blown castor oil M 34 Solids.

Nitrocellulose (7 sec.) oz 25 The water phase is prepared by dissolvingthe sulfonated castor oil in the distilled water, then adding to onegallon of the resulting solution the sodium salt or .sulionated laurylalcohol and the methyl cellulose in the proportion stated. The lacquerphase is made by dissolving the nitrocellulose in the pretdcuslypreparedmixture of solvents and plasticizer. The given proportion of lacquerphase is then emulsified in the water phase by passing the mixturethrough a colloid mill or honi'ogeniz-er.

Coat-mg B glue) Fer cent by weight Crystallized glucose 15 Hide glue(gel. strength 499-415 g.) 15 Water '79 The crystallized glucose andwater are heated in a jacketed kettle with agitation to 176 F. The glueis added and heating is continued between 170 and 180 F. untilthe-mixture is uniiorm and grain-free. The water removed by evaporationis replaced. Preferably 1% of beta naphthol on the weight of the glue orsimilar anti-mold compound is added.

A container of pressed paper pulp sized throughout during manufacturewith 10% of parafiin Wax is first coated with Coating A by filling thecontainer with the lacquer emulsion and immediately pouring it out witha rotary motion. The excess is allowed to drain drip free and thecontainer is then dried for 15 minutes at 150-160 F. or for 2 hours at-130 'F. in a drying chamber equipped with a fan for circulat ing theair. The container is then removed and coated with Coating B which isapplied at a temperature of 160-180" F., the manner of application beingotherwise identical with that of Coating A. The container is then driedfor 16 hours at room temperature and then dried 2 hours at 150460 F. inthe same type of drying chamber as described above.

Exzlmm 2 Coating A The same as in' Example 1.

Coating B (glue) Per cent by weight (dry basis) Invert sugar syrup (50%inverted) 15 Hide glue (gel. strength 400-415 g.).. 15

The coatings are prepared and applied to the paper pulp container inexactly'the same man- Water paper pulp container in exactly the samemanner as that described in Example 1. In making up Coating B theglycerine, cane sugar and water are first heated, the glue being addedlater.

Empress i Coating A.

The same as in Example 1.

floating B er cent by weight (dry basis) Invert sugar syrup (5.0%inverted) l3 Casein 12 Ammonia, 26 1 Water; 7

Weigh the water (less th water in the sugar syrup) into an agitated,jacketed kettle and add the casein; stirring until all lumps aredispersed. r

Add the ammonia and heat slowly (in the course of 40 minutes) withstirring tolfiO" F. Add the invert sugar syrup and stir at -160" F.until homogeneous. Replace evaporated water.

The coatings are applied in exactly the same manner as in Example 1,except that Coating B should be applied at a temperature not exceedingF.

The fibrous containers produced as in Examples 1 to 4 are extremelyimpervious to hydrocarbons and are especially adapted for use asnon-refillable containers for dispensing motor and lubricating oils. Theuse of pressed paper pulp for such containers is extremely advantageoussince it is cheap and seamless. W'hile -reference has been made tocontainers made from such pulp sized with wax, it will be obvious thatcontainers made from unsized pulp or from pup sized with other agents,such as 5% of rosin size, may be used.

EXAMPLE 5 Coating A The same as in Example 1.

- Coating B y Per cent by weight Glucose 7.5 Glycer 7.5 Hide glue (gel.strength 400-415 g.) 15.0 Water 70.0

This coating is made up as in Example 3, the glycerol, glucose andwaterbeing first heated to 170 and the glue being then' added.

Coating A is first uniformly applied by spraying on 16 oz. cotton duck.The coated fabric is dried at 150-460" F. ior thirty'minutes. ThenCoating B at a temperature of 150 -160 1".,is sprayed uniformlyasa-second coat and dried at loo-160 F. for two hours. The fabric thusprepared is extremely resistant to penetration by hydrocarbons, and, forexample, may be us'ed'in the fabrication of hose or tubing through whichgasoline or other hydrocarbons are to be passed.

Coating A The same as in Example 1. Coating B resistance is a primerequisite, provided the tem-' perature to which it is subjected does notexceed 150? F.

hit

This coating was made up by commingling the specified materials andsubjecting them to slight heating while agitating in order to obtain ahomogeneous mixture.'

Coating A was applied to a paper pulp cone exactly as in Example 1.Coating B was then applied over Coating A by adipping operation,followed by draining drip-tree, whereupon the container was dried for 2hours at 140-150" F.

EXAMPLE 8 (Bax-ramp znn wrm Gnocosn) EXAMPLE 9 (Dnx'rm FLnxInmzEb wrrnInvna'r doses) This example is exactly like Example 7 except that 25% ofNulonioline (dry basis) was substituted for the dextrose in thatexample. Nulomoline is an impure invert sugar syrup comprisin to belimited to the above description and specific examples. Thus, anylacquer or. lacquer emulsion any suitable manner.

comprising a cellulose. derivative may be used. Any cellulose ester orethermay be used. Other plasticizers and solvents than those shown maybe used. Compatible resins, either naturalor synthetic, may be added tothe cellulose derivative coating composition. The coats may be appliedin dients,'o rder of mixing and temperatures 0! appli- The proportion ofingre cation, may all be varied considerably without departing from thespirit of the invention. Thus, if desired, instead of the dryingprocedure described ior Coating Bin the examples, the coating of thesuperimposed glue may be dried at atmospherictemperature for a periodo'f'irom 15 minutes to twenty-four hours, preferablyior 16 hours, beforebeing placed in the oven, in order to allow the melting point of theglue mixture to rise above that or the drying oven by evaporation ofwater, or formaldehyde or paraformaldehyde may be added in the glue mixso as to set the glue coating before 11 .1 or the glue-coating may besprayed with aqueous formaldehyde-after its application and prior todrying; When formaldehyde is used in glue coat. it is highly preferredto use .l4-.16% of 100% formaldehyde (CI-I20) calculated on the weightof the glue. If desired, drying of the glue cost at elevatedtemperatures may be altogether eliminated by the use of the specifiedproportion OI formaldehyde and by the expedient of drying at roomtemperature for 16 hours. Other drying temperatures than those specifiedin the examples may be used ii desired. The coatings described in theexamples may be used interchangeably. Thus, pressed paper pulp might beused as the base in Example 5, or fabric as the base in mamples l to lBy "oil, grease and hydrocarbon-resistant as used in the claim is meantimpermeable to and not decomposed by or chemically afiected by oils.greases and hydrocarbons generally, including those herein enumerated.It is not intended to be limited to such hydrocarbons as gasoline andmotor oil to which the invention is particularly applicable. By watermiscible organic binder" as used in the claim, there is meantwatermiscible organic binders of the type herein disclosed and similarmaterials, namely, protein glues such as hide or .bone glue or casein,or the water-soluble gums such as gum arabic, dextrine, etc.- Thesebinders are of the type that :lorm solutions or colloidal suspensionsupon admixture with water. By g1ue" there is meant protein glues such ashide and bone glue, gelatine, casein, albumin, etc.

By "water-soluble gum" is meant such natural gums as are hereindisclosed, dextrine and similar gums which are termed watersoluble bythose skilled in the arts. The terms "a use of a water-miscible organicbinder coating flexibilized with polyhydric alcohols in conjunction witha cellulose derivative coating for rendering materials oil. grease andhydrocarbon-resistant. In co-pending application. Serial Number 111,599,filed Nov. 19, 1936, there is disclosed a coating composition comprisinga water-miscible organic binder fiexlbilized with sorbitol or mixturesof sorbitol and lower polyhydric alcohols.

Having described my invention, what I claim is: An oil, greaseandhydrocarbon-resistant fibrous material comprising a fibrous baseprovided with two superimposed flexible coatings, the first coatingwhich is in contact with the fibrous base being highly resistant tomoisture and consisting essentially of a plasticized cellulosederivative, and the second coating which is superimposed over said firstcoating and which is to be exposed to oil,

grease or hydrocarbon being highly resistant to oils, greases andhydrocarbons and consisting

